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WO2012008490A1 - Procédé de production d'un composé cyclique condensé, et composé brut destiné à être utilisé dans le procédé - Google Patents

Procédé de production d'un composé cyclique condensé, et composé brut destiné à être utilisé dans le procédé Download PDF

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WO2012008490A1
WO2012008490A1 PCT/JP2011/065985 JP2011065985W WO2012008490A1 WO 2012008490 A1 WO2012008490 A1 WO 2012008490A1 JP 2011065985 W JP2011065985 W JP 2011065985W WO 2012008490 A1 WO2012008490 A1 WO 2012008490A1
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group
formula
independently represents
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宏樹 寺井
友也 樫木
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14—Ortho-condensed systems

Definitions

  • the present invention relates to a method for producing a fused ring compound and a raw material compound used in the method.
  • Dithienothiophene derivatives are being studied as organic semiconductor materials.
  • Non-patent Document 1 As a method for producing a dithienothiophene derivative, a first step of dilithiating a 3,3′-dibromo-2,2′-bithiophene derivative, and a product produced in the first step and bis (phenylsulfonyl) sulfide A method (Non-patent Document 1) consisting of a second step in which is reacted is proposed.
  • the conventional method for producing a dithienothiophene derivative has a problem that the yield of the dithienothiophene derivative is low.
  • an object of the present invention is to provide a method for producing a fused ring compound, a typical example of which is a dithienothiophene derivative, in a high yield.
  • the present invention has the formula
  • a ring and B ring each independently represents an aromatic ring.
  • Y represents a Group 15 element or a Group 16 element.
  • Z each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.
  • m represents 0 or 1; When Y is a Group 15 element, m is 1, and when Y is a Group 16 element, m is 0.
  • a transition metal complex In the presence of a transition metal complex,
  • a ring and B ring represent the same meaning as the above.
  • X 1 and X 2 each independently represent a halogen atom, an alkyl sulfonate group or an aryl sulfonate group.
  • M 1 represents an alkali metal atom or a halogenated magnesia group.
  • M 2 represents an alkali metal atom, a halogenated magnesia group or a hydrogen atom.
  • Y, Z and m represent the same meaning as described above.
  • a ring and B ring each independently represents an aromatic ring.
  • Y represents a Group 15 element or a Group 16 element.
  • Z each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.
  • m represents 0 or 1; When Y is a Group 15 element, m is 1, and when Y is a Group 16 element, m is 0.
  • a transition metal complex In the presence of a transition metal complex,
  • M 3 represents a typical metal atom or a halogenated magnesi group.
  • X 2 represents a halogen atom, an alkyl sulfonate group or an aryl sulfonate group.
  • a ring, B ring, Y, Z, and m represent the same meaning as described above.
  • M 3 represents a typical metal atom or a halogenated magnesi group.
  • a ring and B ring each independently represent an aromatic ring.
  • X 2 represents a halogen atom, an alkyl sulfonate group or an aryl sulfonate group.
  • Y represents a Group 15 element or a Group 16 element.
  • Z represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.
  • m represents 0 or 1; When Y is a Group 15 element, m is 1, and when Y is a Group 16 element, m is 0. ] The compound represented by these is provided.
  • a ring and B ring each independently represents an aromatic ring.
  • X 2 represents a halogen atom, an alkyl sulfonate group or an aryl sulfonate group.
  • Y represents a Group 15 element or a Group 16 element.
  • Z each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.
  • m represents 0 or 1; When Y is a Group 15 element, m is 1, and when Y is a Group 16 element, m is 0. ] The compound represented by these is provided.
  • a condensed ring compound whose representative example is a dithienothiophene derivative can be produced in high yield.
  • the first production method of the present invention includes a step of reacting the compound represented by the formula (1) with the compound represented by the formula (2) in the presence of a transition metal complex. It is a manufacturing method of the compound represented by (3).
  • the A ring and the B ring each independently represent an aromatic ring.
  • the aromatic ring may have a substituent.
  • the aromatic ring preferably has 2 to 60 carbon atoms, more preferably 2 to 22 carbon atoms, and still more preferably 3 to 14 carbon atoms.
  • the carbon number does not include the carbon number of the substituent that the aromatic ring has.
  • aromatic ring examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, tetracene ring, pyrene ring, perylene ring, fluorene ring, oxadiazole ring, thiadiazole ring, oxazole ring, thiophene ring, pyrrole ring, furan ring.
  • the A ring and the B ring may form a polycyclic structure via a ring.
  • Examples of such compounds are the compounds of the formula (1-2) and the compounds of the formula (1-34) described later.
  • the A ring and the B ring are preferably each independently an aromatic hetero 5-membered ring.
  • the heterocyclic 5-membered ring may be further condensed with a ring.
  • the halogen atom represented by X 1 and X 2 a fluorine atom, a chlorine atom, a bromine atom, an iodine atom.
  • examples of the alkyl sulfonate group represented by X 1 and X 2 include a methane sulfonate group and a trifluoromethane sulfonate group.
  • examples of the aryl sulfonate group represented by X 1 and X 2 include a benzene sulfonate group and a paratoluene sulfonate group.
  • X 1 and X 2 are preferably a chlorine atom, a bromine atom, and an iodine atom, and more preferably a bromine atom and an iodine atom, from the viewpoint of increasing the reaction yield.
  • Preferred embodiments of the compound represented by the formula (1) are a compound represented by the formula (1A) and a compound represented by the formula (1B).
  • each R 1 independently represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a substituted amino group, a silyl group, A substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an amide group, a heteroaryl group, a carboxyl group, a substituted carboxyl group, a nitro group, or a cyano group is represented.
  • n represents an integer of 0 to 2. Two n may be the same or different.
  • R 1 s When there are a plurality of R 1 s , they may be the same or different. when n is 2, regardless of the definition of R 1, adjacent R 1 may form a cyclic structure together with the carbon atom bonded to each of the R 1 bonded to each other.
  • E each independently represents —O—, —S—, —Se— or —N (R 3 ) —.
  • R 3 each independently represents an alkyl group, an aryl group, or a heteroaryl group. Two E's may be the same or different.
  • X 1 and X 2 represent the same meaning as described above.
  • the cyclic structure corresponds to a saturated or unsaturated monocyclic or polycyclic hydrocarbon ring or heterocyclic ring, and examples thereof include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a naphthalene ring, Examples include a thienothiophene ring, a benzothiophene ring, a cyclopentane ring, and a cyclohexane ring.
  • R 2 each independently represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, or a halogen atom.
  • R 2 When there are a plurality of R 2 , they may be the same or different.
  • R 2 When having a group adjacent carbon atoms in the benzene ring represented by each R 2, regardless of the definition of R 2, R 2 having the adjacent carbon atoms, together with the carbon atom adjacent bonded to each other An annular structure may be formed.
  • E each independently represents —O—, —S—, —Se— or —N (R 3 ) —.
  • R 3 each independently represents an alkyl group, an aryl group, or a heteroaryl group. Two E's may be the same or different.
  • X 1 and X 2 represent the same meaning as described above.
  • the cyclic structure corresponds to a saturated or unsaturated monocyclic or polycyclic hydrocarbon ring or heterocyclic ring, and examples thereof include a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, a naphthalene ring, Examples include a thienothiophene ring, a benzothiophene ring, a cyclopentane ring, and a cyclohexane ring.
  • the carbon number of the alkyl group is usually 1 to 60, preferably 1 to 20.
  • the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group , Octadecyl group, eicosyl group, trifluoromethyl group, perfluorohexyl group, perfluorooctyl group and the like.
  • the number of carbon atoms of the alkoxy group is usually 1 to 60, preferably 1 to 20.
  • Alkoxy groups include methoxy, ethoxy, n-propyloxy, n-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, trifluoro Examples include methoxy group, perfluorohexyloxy group, perfluorooctyloxy group, methoxymethyloxy group, 2-ethoxyethyloxy group and the like.
  • the carbon number of the alkylthio group is usually 1 to 60, preferably 1 to 20.
  • Examples of the alkylthio group include a butylthio group, a hexylthio group, an octylthio group, and a dodecylthio group.
  • An aryl group is an atomic group obtained by removing one hydrogen atom bonded to a ring carbon atom from an aromatic hydrocarbon, and includes a group having a benzene ring and a group having a condensed ring.
  • the aryl group may have a substituent, and the aryl group excluding the substituent usually has 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms.
  • the aryl group includes a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a 1-tetracenyl group, a 2-tetracenyl group, a 5-tetracenyl group, 1- Pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-perenyl group, 3-perylenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 1-biphenylenyl group, 2-biphenylenyl group, 2- Examples include phenanthrenyl group and 9-phenanthrenyl group.
  • the aryloxy group may have a substituent, and the aryloxy group excluding the substituent usually has 6 to 60 carbon atoms, and preferably 6 to 20 carbon atoms.
  • the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a pentafluorophenyloxy group.
  • the arylthio group may have a substituent, and the arylthio group excluding the substituent usually has 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms.
  • the arylthio group include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a pentafluorophenylthio group.
  • the alkenyl group may have a substituent, and the carbon number of the alkenyl group excluding the substituent is usually 2 to 60, preferably 2 to 20.
  • Examples of the alkenyl group include a vinyl group, a 1-octenyl group, and a 2-phenylvinyl group.
  • the alkynyl group may have a substituent, and the carbon number of the alkynyl group excluding the substituent is usually 2 to 60, preferably 2 to 20.
  • Examples of the alkynyl group include ethynyl group, 1-octynyl group, 2-phenylethynyl group, and trimethylsilylethynyl group.
  • the substituted amino group usually has 1 to 60 carbon atoms, preferably 2 to 48 carbon atoms.
  • substituted amino groups include methylamino group, dimethylamino group, ethylamino group, diethylamino group, dipropylamino group, phenylamino group, diphenylamino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino Group, pyridylamino group and the like.
  • the substituted silyl group usually has 1 to 60 carbon atoms, preferably 3 to 48 carbon atoms.
  • Examples of the substituted silyl group include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a triphenylsilyl group, a tribenzylsilyl group, a diphenylmethylsilyl group, and a dimethylphenylsilyl group.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • Acyl groups usually have 2 to 20 carbon atoms.
  • Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a benzoyl group, a trifluoroacetyl group, and a pentafluorobenzoyl group.
  • Acyloxy groups usually have 2 to 20 carbon atoms.
  • Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, a benzoyloxy group, a trifluoroacetyloxy group, and a pentafluorobenzoyloxy group.
  • the amide group usually has 2 to 20 carbon atoms.
  • Examples of the amide group include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, a diacetamide group, and a dibenzamide group.
  • the heteroaryl group may have a substituent, and the carbon number of the heteroaryl group excluding the substituent is usually 3 to 60, preferably 3 to 20.
  • Heteroaryl groups include 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-oxazolyl group, 2-thiazolyl group, 2-imidazolyl group 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-benzofuryl group, 2-benzothienyl group, 2-thienothienyl group and the like.
  • the substituted carboxyl group usually has 2 to 20 carbon atoms.
  • Examples of the substituted carboxyl group include a methyl carboxylate group, an ethyl carboxylate group, and a phenyl carboxylate group.
  • each E is independently preferably —O—, —S— or —Se—, more preferably —S—.
  • each E is independently preferably —O—, —S—, or —Se—, more preferably —S—.
  • Examples of the compound represented by the formula (1) include the following compounds.
  • examples of the alkali metal atom represented by M 1 include a lithium atom, a sodium atom, and a potassium atom.
  • examples of the halogenated magnetio group represented by M 1 include a magnesium chloride group, a magnesium bromide group, and a magnesium iodide group.
  • examples of the alkali metal atom represented by M 2 include a lithium atom, a sodium atom, and a potassium atom.
  • examples of the halogenated magnetio group represented by M 2 include a magnesium chloride group, a magnesium bromide group, and a magnesium iodide group.
  • an alkali metal atom and a halogenated magnesia group are preferable.
  • M 1 and M 2 are preferably the same from the viewpoint of availability of raw materials and ease of preparation of the raw materials.
  • the group 15 element represented by Y is exemplified by nitrogen, phosphorus, and arsenic.
  • the group 16 element represented by Y is exemplified by oxygen, sulfur and selenium.
  • Y is preferably a Group 16 element, and more preferably sulfur.
  • the definition and specific examples of the alkyl group, aryl group, and heteroaryl group represented by Z are the alkyl group, aryl group, and heteroaryl group represented by R 1 in the formula (1A). Definitions and specific examples are the same.
  • m 0 or 1.
  • Y is a Group 15 element
  • m is 1
  • Y is a Group 16 element
  • the compound represented by the formula (2) may be an anhydride or a hydrate.
  • sodium sulfide pentahydrate and sodium sulfide nonahydrate are also included in the compound represented by the formula (2).
  • the amount of the compound represented by the formula (2) is 1 mol or more and 1 to 100 mol with respect to 1 mol of the compound represented by the formula (1).
  • the amount is preferably 1 to 10 mol.
  • the amount of the compound represented by the formula (2) is 1 mol or less with respect to 1 mol of the compound represented by the formula (1), the amount of Y for forming a condensed ring is insufficient, resulting in condensation.
  • the yield of the ring compound may decrease.
  • Examples of the compound represented by the formula (2) include the following compounds.
  • a ring, B ring, Y, Z, m represents the same meaning as A ring, B ring, Y, Z, m in said formula (1).
  • the compound represented by the formula (3A) can be produced by reacting the compound represented by the formula (1A) with the compound represented by the formula (2) in the presence of a transition metal complex. it can.
  • R 1 , n, Y, Z, m and E represent the same meaning as described above.
  • the compound represented by the formula (3B) can be produced by reacting the compound represented by the formula (1B) with the compound represented by the formula (2) in the presence of a transition metal complex. it can.
  • R 2 , p, Y, Z, m and E represent the same meaning as described above.
  • Examples of the compound represented by the formula (3) include the following compounds.
  • Preferred embodiments of the compound represented by the formula (5) are a compound represented by the formula (5A) and a compound represented by the formula (5B).
  • each R 1 independently represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a substituted amino group, a silyl group, A substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an amide group, a heteroaryl group, a carboxyl group, a substituted carboxyl group, a nitro group, or a cyano group is represented.
  • n represents an integer of 0 to 2. Two n may be the same or different.
  • R 1 s When there are a plurality of R 1 s , they may be the same or different. when n is 2, regardless of the definition of R 1, adjacent R 1 may form a cyclic structure together with the carbon atom bonded to each of the R 1 bonded to each other.
  • E each independently represents —O—, —S—, —Se— or —N (R 3 ) —.
  • R 3 each independently represents an alkyl group, an aryl group, or a heteroaryl group. Two E's may be the same or different.
  • Y, Z, m and X 2 are as defined above.
  • R 2 each independently represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, or a halogen atom.
  • R 2 When there are a plurality of R 2 , they may be the same or different.
  • R 2 When having a group adjacent carbon atoms in the benzene ring represented by each R 2, regardless of the definition of R 2, R 2 having the adjacent carbon atoms, together with the carbon atom adjacent bonded to each other An annular structure may be formed.
  • E represents —O—, —S—, —Se— or —N (R 3 ) —.
  • R 3 represents an alkyl group, an aryl group, or a heteroaryl group.
  • Two E's may be the same or different.
  • Y, Z, m and X 2 are as defined above.
  • each E is independently preferably —O—, —S— or —Se—, more preferably —S—.
  • each E is independently preferably —O—, —S— or —Se—, more preferably —S—.
  • Examples of the compound represented by the formula (5) include the following compounds.
  • M 3 represents a typical metal atom or a halogenated magnesi group.
  • Y, Z, m, X 2 , A ring and B ring have the same meaning as described above.
  • alkali metal examples include lithium and sodium.
  • alkali metal hydride examples include lithium hydride and sodium hydride.
  • alkyl metal examples include methyl lithium and butyl lithium.
  • alkyl magnesium halide examples include methyl magnesium chloride, ethyl magnesium chloride, methyl magnesium bromide, and ethyl magnesium bromide.
  • the compound represented by the formula (3) can be produced using the compound represented by the formula (4). Details will be described later in the section of the second production method of the present invention.
  • the compound represented by formula (4), in which M 3 is an alkali metal or a halogenated magnesi group, is produced as a reaction intermediate in the first production method of the present invention.
  • the second production method of the present invention includes the step of intramolecular cyclization reaction of the compound represented by the formula (4) in the presence of a transition metal complex, the production of the compound represented by the above formula (3). Is the method.
  • the typical metal atom represented by M 3 is preferably an alkali metal atom.
  • the alkali metal atom include a lithium atom, a sodium atom, and a potassium atom.
  • examples of the magnesium halide represented by M 3 include magnesium chloride, magnesium bromide, magnesium iodide and the like.
  • Preferred embodiments of the compound represented by the formula (4) are a compound represented by the formula (4A) and a compound represented by the formula (4B).
  • each R 1 independently represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a substituted amino group, a silyl group, A substituted silyl group, a halogen atom, an acyl group, an acyloxy group, an amide group, a heteroaryl group, a carboxyl group, a substituted carboxyl group, a nitro group, or a cyano group is represented.
  • n represents an integer of 0 to 2. Two n may be the same or different.
  • R 1 s When there are a plurality of R 1 s , they may be the same or different. when n is 2, regardless of the definition of R 1, adjacent R 1 may form a cyclic structure together with the carbon atom bonded to each of the R 1 bonded to each other.
  • E each independently represents —O—, —S—, —Se— or —N (R 3 ) —.
  • R 3 each independently represents an alkyl group, an aryl group, or a heteroaryl group. Two E's may be the same or different.
  • Y, M 3 , Z, m and X 2 represent the same meaning as described above.
  • R 2 each independently represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, or a halogen atom.
  • R 2 When there are a plurality of R 2 , they may be the same or different.
  • R 2 When having a group adjacent carbon atoms in the benzene ring represented by each R 2, regardless of the definition of R 2, R 2 having the adjacent carbon atoms, together with the carbon atom adjacent bonded to each other An annular structure may be formed.
  • E each independently represents —O—, —S—, —Se— or —N (R 3 ) —.
  • R 3 each independently represents an alkyl group, an aryl group, or a heteroaryl group. Two E's may be the same or different.
  • Y, M 3 , Z, m and X 2 represent the same meaning as described above.
  • each E is independently preferably —O—, —S— or —Se—, more preferably —S—.
  • each E is independently preferably —O—, —S—, or —Se—, more preferably —S—.
  • Examples of the compound represented by the formula (4) include the following compounds.
  • the transition metal complex used in the first production method and the second production method of the present invention is preferably a transition metal complex containing a Group 8 to 10 element, more preferably a transition metal complex containing a Group 10 element. Further, palladium complexes and nickel complexes are more preferable, and palladium complexes are particularly preferable.
  • the transition metal complex preferably has at least one phosphine ligand.
  • the transition metal complex includes a transition metal complex precursor.
  • the transition metal complex precursor is a composition that is converted into a transition metal complex in the reaction system, and represents a composition that includes a precursor transition metal complex and a phosphine ligand or phosphonium salt.
  • Examples of the palladium complex include tetrakis (triphenylphosphine) palladium (0), tetrakis (tristolylphosphine) palladium (0) (including various substituted isomers of ortho, meta, and para), bis (triphenylphosphine) palladium.
  • (II) dichloride bis (tricyclohexylphosphine) palladium (II) dichloride, bis (triethylphosphine) palladium (II) dichloride, [1,2-bis (diphenylphosphino) ethane] palladium (II) dichloride, [1, 1'-bis (difilphosphino) ferrocene] palladium (II) dichloride, bis (acetonitrile) palladium (II) dichloride, bis (benzonitrile) palladium (II) dichloride, and the like.
  • tetrakis (triphenylphosphine) palladium (0) and tetrakis (tristolylphosphine) palladium (0) are preferable.
  • nickel complex examples include tetrakis (triphenylphosphine) nickel (0), bis (triphenylphosphine) nickel (II) dichloride, [1,2-bis (diphenylphosphino) ethane] nickel (II) dichloride, [1 , 3-Bis (diphenylphosphino) propane] nickel (II) dichloride, [1,4-bis (diphenylphosphino) butane] nickel (II) dichloride, [1,1′-bis (difilphosphino) ferrocene ] Nickel (II) dichloride etc. are mentioned.
  • transition metal complex for the precursor examples include Pd 2 (dba) 3 (where dba represents trans, trans-dibenzylideneacetone), Pd (dba) 2 , palladium (II) acetate, bis (1, 5-cyclooctadiene) nickel (0) and the like.
  • Pd 2 (dba) 3 , Pd (dba) 2 , and palladium (II) acetate are preferable.
  • phosphine ligand examples include trialkylphosphines such as tri-n-butylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, tricyclopentylphosphine, tribenzylphosphine, triphenylphosphine, and tritolylphosphine (ortho , Meta, and para substituted isomers), tris (methoxyphenyl) phosphine (including ortho, meta, and para substituted isomers), and other triarylphosphines, and diarylalkyl phosphines such as diphenylcyclohexylphosphine Phosphines, dicyclohexylphenylphosphine, (2-biphenylyl) di-tert-butylphosphine and other dialkylarylphosphines, 1,2-bis (diphenylphosphino) ethane, 1,3
  • tri-tert-butylphosphine tricyclohexylphosphine, and (2-biphenylyl) di-tert-butylphosphine are preferable.
  • the phosphonium salt is a salt of the phosphine ligand and an acid such as HBF 4 , HPF 6 , HSbF 6 and the like, and includes tri-n-butylphosphonium tetrafluoroborate, tri-tert-butylphosphonium tetrafluoroborate, triphenylphosphonium. Examples include hexafluorophosphate and triphenylphosphonium hexafluoroantimonate. Of these, tri-tert-butylphosphonium tetrafluoroborate is preferable.
  • a base may be further added to convert the phosphonium salt into a phosphine ligand in the reaction solution.
  • Examples of the base include sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, sodium carbonate, potassium carbonate, cesium carbonate, sodium fluoride, potassium fluoride, sodium phosphate and potassium phosphate. Of these, sodium carbonate, potassium carbonate, and cesium carbonate are preferable.
  • the amount of the transition metal complex and the precursor transition metal complex used is adjusted so that an appropriate amount of transition metal is present in the reaction system.
  • An appropriate amount of the transition metal in the reaction system is 1 mol of the compound represented by the formula (1), formula (1A), formula (1B), formula (4), formula (4A) or formula (4B). 0.0001 to 10 mol, preferably 0.001 to 1 mol, more preferably 0.01 to 0.5 mol.
  • the amount of the transition metal complex used is 0 with respect to 1 mol of the compound represented by the formula (1), formula (1A), formula (1B), formula (4), formula (4A) or formula (4B).
  • the amount is preferably from 0.0001 to 10 mol, more preferably from 0.001 to 1 mol.
  • the amount of the transition metal complex for precursor used is 1 mol of the compound represented by the formula (1), formula (1A), formula (1B), formula (4), formula (4A) or formula (4B).
  • the amount is preferably 0.0001 to 10 mol, more preferably 0.001 to 1 mol.
  • the amount of the phosphine ligand used is preferably 1 to 10 mol, more preferably 1 to 4 mol, relative to 1 mol of the transition metal complex for precursor.
  • the amount of the phosphonium salt used is preferably 1 to 10 mol, more preferably 1 to 4 mol, relative to 1 mol of the precursor transition metal complex.
  • the amount of the base used is preferably 1 to 10 mol, more preferably 1 to 5 mol, relative to 1 mol of the phosphonium salt.
  • a transition metal complex may be used individually by 1 type, or may use 2 or more types together.
  • the transition metal complex can be added sequentially by dividing the amount to be added to the reaction system into multiple times.
  • the reaction rate may drop after a certain time has elapsed after the addition of the transition metal complex, but the reaction rate can be increased by further adding the transition metal complex in this state.
  • the reaction temperature in the first production method and the second production method of the present invention is preferably 20 to 300 ° C. From the viewpoint of allowing the reaction to proceed efficiently, 50 ° C or higher is more preferable, and 80 ° C or higher is more preferable. Moreover, from a viewpoint of suppressing a side reaction, 250 degrees C or less is more preferable, and 200 degrees C or less is further more preferable.
  • the reaction time is usually 1 minute to 200 hours. From the viewpoint of sufficiently allowing the reaction to proceed, one hour or longer is preferable.
  • the reaction may be performed in the absence of a solvent or in the presence of a solvent, but is preferably performed in the presence of a solvent.
  • the solvent should just be a reaction inert solvent, and may be used individually by 1 type, or may be used as a some mixed solvent.
  • the solvent examples include aliphatic hydrocarbon solvents such as cyclohexane and methylcyclohexane, aromatic hydrocarbon solvents such as benzene and toluene, ether solvents such as tetrahydrofuran and anisole, 1-methyl-2-pyrrolidone, N, N—
  • aliphatic hydrocarbon solvents such as cyclohexane and methylcyclohexane
  • aromatic hydrocarbon solvents such as benzene and toluene
  • ether solvents such as tetrahydrofuran and anisole
  • 1-methyl-2-pyrrolidone 1-methyl-2-pyrrolidone
  • N, N— examples include aprotic polar solvents such as dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, and acetonitrile, and water.
  • Aromatic hydrocarbon solvents, ether solvents, and aprotic polar solvents are preferred.
  • the reaction may be performed in air or in an inert gas atmosphere, but is preferably performed in an inert gas atmosphere such as nitrogen or argon.
  • the compound represented by the formula (1), the compound represented by the formula (2), the transition metal complex, and the solvent are added to the vessel and mixed. .
  • the resulting mixture is reacted at the desired temperature.
  • the reaction product obtained can be obtained by concentrating it as it is or by putting the reaction product in water and extracting it with an organic solvent such as toluene, ethyl acetate, diethyl ether, dichloromethane or the like.
  • the desired compound represented by formula (3) is obtained by concentrating the organic layer.
  • this compound may be purified by column chromatography, extraction, recrystallization or distillation.
  • the transition metal complex represented by M is oxidatively added to the compound represented by the formula (1) to yield a compound represented by the following formula (6).
  • the compound represented by the following formula (6) undergoes a metal exchange reaction with the compound represented by the above formula (2) to yield a compound represented by the following formula (7).
  • the transition metal complex M is reductively eliminated from the compound represented by the following formula (7) to produce a compound represented by the formula (4), wherein M 3 is an alkali metal or a halogenated magnesium group.
  • M 3 is an alkali metal or a halogenated magnesium group.
  • M represents a transition metal complex.
  • M 1 , M 2 , Y, Z, m, X 1 , X 2 , A ring and B ring have the same meaning as described above.
  • the transition metal complex represented by M is oxidatively added to the compound represented by the formula (4) to yield a compound represented by the following formula (8).
  • a compound represented by the following formula (8) undergoes a metal exchange reaction in the molecule to yield a compound represented by the following formula (9).
  • the transition metal complex M is reductively eliminated from the compound represented by the following formula (9) to produce the compound represented by the formula (3), and at the same time, the transition metal complex M is regenerated.
  • M represents a transition metal complex.
  • M 1 , M 2 , Y, Z, m, X 1 , X 2 , A ring and B ring have the same meaning as described above.
  • the compound represented by the formula (1) and the compound represented by the formula (2) are represented by the formula (4) in the reaction system.
  • the compound represented by the formula (3) is produced via the compound.
  • the compound represented by the formula (3) can be produced from the compound represented by the formula (1) and the compound represented by the formula (2) in the presence of a transition metal complex.
  • the compound represented by the formula (3) can also be produced from the compound represented by the formula (4) in the presence of a transition metal complex.
  • the suitable thickness of the organic thin film varies depending on the element to which the organic thin film is applied, but is usually in the range of 1 nm to 100 ⁇ m, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and more preferably 20 nm to More preferably, it is 200 nm.
  • An organic thin film having such a thickness makes it easy to form an organic thin film element having good charge transport properties and sufficient strength.
  • the organic thin film may contain one kind of the compound represented by the formula (3) alone or may contain two or more kinds.
  • an organic thin film contains components other than the compound represented by the said Formula (3), it is preferable that the compound represented by the said Formula (3) is included 10 mass% or more, and more than 30 mass% is included. preferable.
  • the content of the compound represented by the formula (3) is less than 30% by mass, it tends to be difficult to form a thin film or to obtain good charge mobility.
  • components other than the compound represented by the formula (3) include organic semiconductor materials other than the compound represented by the formula (3).
  • Organic thin film element Since the organic thin film of the present invention can exhibit high charge transportability, it can transport charges injected from electrodes provided in the organic thin film element or charges generated by light absorption. Utilizing these characteristics, it can be applied to organic thin film elements such as organic thin film transistors, organic solar cells, photosensors, and organic electroluminescence displays.
  • the HPLC area percentage value was a value in a chromatogram detected at a wavelength of 254 nm by high performance liquid chromatography (HPLC, trade name: LC-20AD, manufactured by Shimadzu Corporation).
  • HPLC high performance liquid chromatography
  • the compound to be measured was dissolved in tetrahydrofuran, and 0.5 ⁇ L of the solution obtained by HPLC was injected.
  • As the mobile phase of HPLC 0.1% aqueous acetic acid solution (liquid A) and acetonitrile (liquid B) with 0.1% acetic acid added were used, and the volume of liquid A with respect to liquid B at a flow rate of 0.5 mL / min.
  • a Shim-pack XR-ODS inner diameter 2.0 mm ⁇ length 75 mm (manufactured by Shimadzu Corporation) was used.
  • a detector a photodiode array detector (manufactured by Shimadzu Corporation, trade name: SPD-M20A) was used.
  • Mass spectrometry In the examples, the value of mass spectrometry was determined by AccuTOF TLC JMS-T100TD (manufactured by JEOL Ltd.).
  • NMR analysis The NMR measurement was performed by dissolving the compound in deuterated chloroform and using an NMR apparatus (Varian, INOVA300).
  • the reaction solution was subjected to HPLC analysis, and the area percentage was determined. As a result, the area of the compound (3-8) was 63%, and the area of the compound (1-11) was 34%.
  • the reaction solution was subjected to HPLC analysis, and the area percentage was determined. As a result, the area of the compound (3-8) was 64%, and the area of the compound (1-11) was 0%.
  • the reaction solution was poured into 100 mL of water to obtain a precipitate.
  • the precipitate was collected by filtration and washed with methanol to obtain a solid.
  • the obtained solid was purified using a silica gel column to obtain 0.19 g of compound (3-8). The yield was 53%.
  • Example 3 Mass spectrometry of reaction intermediate of compound (3-8) In Example 3, mass spectrometry was performed on the reaction solution 21 hours after the start of the reaction. As a result, a fragment having an m / z of 529.96 was obtained.
  • the fragment whose m / z is 529.96 is derived from the mass number of the compound corresponding to the compound represented by the formula (7) and the compound represented by the formula (8) described in the reaction mechanism section. It is a measurement result which shows presence of the compound represented by said Formula (4) as a reaction mechanism mentioned above and an intermediate body.
  • the structure of the detected mass number is a compound added with sodium represented by the following formula. Both have the same mass number of 528.73. It is presumed that phosphine is coordinated to palladium in the following formula in the reaction solution.
  • the reaction solution was concentrated, toluene and water were added, and the toluene solution was extracted.
  • the toluene solution was concentrated.
  • the concentrated solution was purified using a silica gel column to obtain 1.9 g of 6-octylbenzo [b] thiophene. The yield was 52%.
  • 6-octylbenzo [b] thiophene (1.9 g, 7.6 mmol) and diethyl ether (37 mL) were placed in a 100 mL flask in which the gas in the flask was replaced with argon. Thereafter, butyl lithium (2.6 M, 3.8 mL) was dropped into the flask. After completion of the dropwise addition, the mixture was heated to reflux for 2 hours. The reaction solution was cooled to 0 ° C., copper (II) chloride (1.5 g, 11 mmol) was added, and then heated to reflux for 2 hours.
  • the reaction solution was filtered, the organic compound in the filtrate was dissolved in toluene (200 mL) and tetrahydrofuran (50 mL), and the resulting solution was added to the filtrate. Thereafter, the filtrate was washed with an acetic acid aqueous solution and water. The filtrate was concentrated, the concentrate was poured into methanol, and the resulting precipitate was collected by filtration to obtain 1.1 g of 6,6'-dioctyl-2,2'-di (benzo [b] thiophene). The yield was 58%.
  • the concentrated organic layer was purified using a silica gel column to obtain 0.70 g of 3,3′-dibromo-6,6′-dioctyl-2,2′-di (benzo [b] thiophene. Yield was 53%.
  • the reaction solution was subjected to HPLC analysis, and the area percentage was determined. As a result, the area of the compound (3-8) was 33%, and the area of the compound (1-11) was 41%.
  • reaction solution was brought to room temperature (25 ° C.), and an aqueous ammonium chloride solution was added.
  • Chloroform was added to extract the organic layer.
  • the chloroform solution as the organic layer was washed with an aqueous ammonium chloride solution, dried using magnesium sulfate, and concentrated.
  • the concentrated solution is poured into a mixed solution of toluene and hexane for reprecipitation, and the resulting precipitate is recrystallized using hot chloroform to obtain thieno [3,2-b: 4,5-b ′] bisbenzo [ b] 21 mg of thiophene was obtained.
  • the yield was 6%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne la production d'un dérivé dithiénothiophène avec un rendement élevé. L'invention concerne en particulier un procédé de production d'un composé représenté par la formule (3) [dans laquelle les cycles A et B représentent indépendamment un cycle aromatique; Y représente un élément appartenant au groupe 15 ou au groupe 16; Z représente un atome d'hydrogène ou équivalent; et m représente 0 ou 1], qui comprend une étape consistant à faire réagir un composé représenté par la formule (1) [dans laquelle les cycles A et B sont tels que définis ci-dessus; et X1 et X2 représentent indépendamment un atome d'halogène ou équivalent] avec un composé représenté par la formule (2) M1M2Y(Z)m (2) [dans laquelle Y, Z et m sont tels que définis ci-dessus; et M1 et M2 représentent indépendamment un métal alcalin ou équivalent] en présence d'un complexe métallique de transition.
PCT/JP2011/065985 2010-07-13 2011-07-13 Procédé de production d'un composé cyclique condensé, et composé brut destiné à être utilisé dans le procédé Ceased WO2012008490A1 (fr)

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